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EP2190885B1 - Method for producing carboxylated ethylene polymer blends - Google Patents

Method for producing carboxylated ethylene polymer blends Download PDF

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Publication number
EP2190885B1
EP2190885B1 EP08801310A EP08801310A EP2190885B1 EP 2190885 B1 EP2190885 B1 EP 2190885B1 EP 08801310 A EP08801310 A EP 08801310A EP 08801310 A EP08801310 A EP 08801310A EP 2190885 B1 EP2190885 B1 EP 2190885B1
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EP
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Prior art keywords
ethylene
pbw
lldpe
hdpe
olefin
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EP08801310A
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German (de)
French (fr)
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EP2190885A2 (en
Inventor
Klaus Besser
Jochen Gerecke
Lutz HÄUSSLER
Bianka Leitner
Inno Rapthel
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/36—Polymerisation in solid state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene

Definitions

  • the invention relates to a process for the preparation of carboxylated ethylene polymer blends composed of at least two different ethylene homopolymers and / or copolymers, in two stages and their use as adhesion promoters in plastic-metal composites.
  • carboxylated olefin polymers based on polyethylenes of different densities (LDPE, MDPE, HDPE), ethylene / ⁇ , ⁇ -ethylenically unsaturated C 3 - to C 12 - Olefin copolymers (LLDPE, POE) or else propylene homo- (HPP) and also random (random) and heterophasic propylene copolymers (RCP, HCP), ethylene / propylene copolymers (EPC) or ethylene / propylene / diene terpolymers (EPDM), generally prepared by reactive extrusion at high temperatures (150-300 ° C) by grafting a carboxyl group-containing monomer such as acrylic acid, fumaric acid and especially maleic anhydride onto the olefinic backbone polymer in the presence of a radical-forming peroxidic initiator ( WO 91)
  • Particularly suitable backbone polymers for this purpose are partially crystalline olefin polymers which, in the amorphous phase which forms between their glass and melting point, permit high diffusion rates for low molecular weight compounds such as acid or anhydride monomers, one of the prerequisites for their high graft polymerization rates.
  • Amorphous and low crystalline olefin elastomers with special morphology are also useful as polymer backbones for free radical solid phase graft modification under certain polymerization conditions (EP 0642538 B1 . EP 0805827 B1 ), but without the properties required for use as a highly effective adhesion promoter, in particular for demanding metal / plastic composites.
  • carboxylated (maleated) high density polyethylenes (HDPE) or branched low density polyethylenes (LDPEs) are primarily carboxylated linear low density ethylene copolymers, either with a low C 3 to C 12 olefin comonomer content below 15% by mass (LLDPE) or with a higher C 3 to C 12 olefin comonomer content (above 15% by mass, POE), in particular ethylene / octene (C 8 ) copolymers (EOC), as well as predominantly propylene units existing random-propylene / ethylene copolymers which, for the purpose of their carboxylation, are prepared exclusively by melt-grafting, preferably using MSA as grafting agent ( US 5,346,963 .
  • melt-carboxylated (-maleinated) ethylene / vinyl acetate (EVA) or ethylene / (meth) acrylic acid ester copolymers (E (M) AE) are used ( EP 0266994 A2 .
  • WO 93/01052 A1 melt-carboxylated (-maleinated) ethylene / vinyl acetate (EVA) or ethylene / (meth) acrylic acid ester copolymers
  • a crystalline polyolefin for. HDPE or LLDPE
  • an amorphous or low crystalline olefin copolymer e.g. B. ethylene / propylene rubber (EPM) known ( EP 0501762 B1 ).
  • melt-grafted ethylene homo- and copolymers and graft-modified olefinic elastomers are their high molecular weights, which are formed during the grafting reaction and which have a negative effect especially when used as adhesives, and the overall costly measures for the removal of residual monomer (s ).
  • the object of the present invention was - while avoiding the disadvantages described - a process for the preparation of a coupling agent (adhesive) based on the carboxylation of polyethylenes (HDPE, LDPE) and / or ethylene / ⁇ , ⁇ -ethylenically unsaturated C 3 - to C To develop 12- olefin copolymers (EPC, LLDPE, POE).
  • a coupling agent adheresive
  • the present invention is a process for preparing carboxylated ethylene polymer blends in two stages, wherein in a first stage in a fluid mixing reactor to 100 parts by mass solid-fluid particulate ethylene polymer with MFR (190 ° C / 2.16 kg support weight) ⁇ 20 g / 10 min, selected from ethylene homopolymers and / or linear ethylene copolymers of composition ⁇ 80 to 98% by mass of ethylene / 2 to ⁇ 20% by mass of C 3 to C 12 olefin units, 0.05 to 15 parts by mass of an ⁇ , ⁇ -ethylenic unsaturated mono- and / or dicarboxylic acid or its anhydride (carboxyl monomer) or a monomer mixture containing at least one carboxyl monomer and 0.01 to 10 parts by weight of a free radical initiator having a 1-hour half-life temperature (T HW / 1h ) between 50 and 200 ° C or corresponding initiator mixture added and graft polymerized at
  • an olefinic elastomer selected from among the elastomeric polypropylenes (ELPP) or random propylene copolymers containing from 5 to 50% by weight of ethylene and / or ⁇ , ⁇ -ethylenically unsaturated C 4 to C 8 olefin and / or diene units is most commonly used , preferably 10 to 25% by mass of ethylene units (PER), or ethylene copolymers having ⁇ 20% by mass of ⁇ , ⁇ -ethylenically unsaturated C 3 to C 12 olefin units (EOR), preferably propylene, butene, hexene or Methyl pentene or octene units, more preferably with 25 to 50 mass% of propylene (EPR *), butene-1 (EBR *) or octene-1 units (EOR *), or an ethylene / vinyl acetate (EVA) or an ethylene / (meth) acrylic acid ester copo
  • the addition of the olefinic elastomer can be omitted (special embodiment based on 0 parts by mass of elastomer).
  • the linear high density polyethylenes are between 0.940 and 0.965 g / cm 3 (HDPE) and linear ethylene / ⁇ 15 mass% of low density C 3 to C 12 olefin copolymers ⁇ 0.940 g / cm 3 (LLDPE), generally by known coordinate coordination techniques using Ziegler and Ziegler-Natta catalysts, respectively - or Phillips-type generated.
  • the ethylene copolymers having high C 3 to C 12 olefin content ⁇ 15% by mass EOP, EOR
  • the olefin elastomers composed mainly of propylene units, such as especially PER, and elastomeric polypropylenes (ELPP) are known to be used made of special metallocene catalyst systems.
  • blends consisting of at least two different ethylene (co) polymers, in particular for the melt-grafting stage, in the form of compounds or reactor blends, is a suitable embodiment of the process according to the invention, according to which a blend of 10-90% by weight % LDPE or LLDPE and 90-10% by mass HDPE, preferably from 20-80% by mass LLDPE and 80-20% by mass HDPE, with MFR (190 ° C / 2.16 kg) ⁇ 20 g / 10 min , the reactor, preferably a twin-screw kneader (DSK), is used.
  • a twin-screw kneader a twin-screw kneader
  • the carboxyl monomer preferably maleic anhydride (MSA) and / or acrylic acid (AS), can also be used as a mixture with a comonomer from the group of vinyl aromatics, preferably styrene, and / or the C 1 to C 12 alkyl esters of acrylic or methacrylic acid, preferably methyl methacrylate (MMA) or methyl (MA) or Ethyl (EA) or butyl acrylate (BA), corresponding compositions 99-20% by mass of carboxyl and 1-80% by mass of comonomer, preferably 90-50% by mass of MSA and / or AS and 10-50% by mass of styrene , be used in the solid phase stage.
  • MMA methyl methacrylate
  • MA methyl
  • EA Ethyl
  • BA butyl acrylate
  • the radically initiated two-stage grafting is advantageously carried out using a free-radical generator or preferably consisting of at least two different radical formers using organic peroxides having half-life temperatures after one hour T HW / 1h between 50 and 200 ° C or to achieve uniform grafting.
  • T HW / 1min between 85 and 250 ° C (measured in 0.1 molar monochlorobenzene solution) in a concentration based on the total ethylene polymer graft substrate amount between 0.001 and 5 mass%, preferably between 0.02 and 2 Mass%, performed.
  • dialkyl peroxydicarbonates having a 1 hour half life temperature (T HW / 1h ) between 55 and 66 ° C, preferably dibutyl peroxydicarbonate (DBPOC) and dicetyl peroxydicarbonate (DCPOC) with T HW / 1h of 65 ° C, dilauroyl peroxide (DLPO ) with T HW / 1h of 80 ° C, dibenzoyl peroxide (DBPO) with T HW / 1h of 91 ° C, tert-butyl peroxy-2-ethylhexanoate (TBPEH) with T HW / 1h of 91 ° C, tert-butyl peroxy -isobutyrate (TBPIB) with T HW / 1h of 98 ° C, 1,1-di- (tert-butylperoxy) -cyclohexane (DTBPC) with T
  • T HW / 1h
  • a preferred embodiment of the process for producing carboxylated ethylene copolymers or ethylene copolymer blends is that in the first stage to 100 parts by weight of particulate ethylene polymer with MFR (190 ° C / 2.16 kg) between 20 and 1000 g / 10 min, selected from a Ethylene homopolymer (HDPE-NM w , LDPE-NM w ) and / or linear ethylene copolymer of composition ⁇ 90 to 98% by mass ethylene / 2 to ⁇ 10% by mass C 3 to C 8 olefin units (LLDPE * -NM w ), 0.2 to 12 parts by weight of MSA, alone or as a monomer mixture with 0.02 to 6 parts by weight of styrene, with the addition of 0.05 to 5 parts by weight of one of at least two radical-forming Initiators with different 1-hour half-life temperatures (T HW / 1h ) between 50 and 120 ° C and between 120 and 180 ° C existing mixture at reaction temperatures between
  • the olefinic elastomer is used for the stabilizer / antioxidant required for the entire carboxylated ethylene polymer blend, in or on which it has been dispersed by means of a separate mixing technology.
  • Stabilizing agents and / or antioxidants are the substances known for olefinic polymers and elastomers, especially primary antioxidants based on sterically hindered phenol compounds, in an amount of from 0.01 to 5 parts by weight, preferably from 0.1 to 2 parts by weight, based on 100 parts by weight of olefin elastomer. used. Also, combinations of at least one primary and one secondary antioxidant, such as. B. systems of a sterically hindered phenol and a phosphite compound can be used.
  • the graft-modified ethylene polymer blends having a degree of carboxylation between 0.05 and 1% by weight, preferably between 0.1 and 0.6% by weight can be used as adhesion promoters and / or adhesives for various substrates, preferably on and between metallic surfaces ,
  • reaction mixture is dispersed in a nitrogen atmosphere at a stirring speed of 400 min -1 with simultaneous increase in temperature at a heating rate of 1.2 ° C / min and upon reaching the final reaction temperature T R1 of 70 ° C over a time t R1 of 60 min held on T R1 .
  • the solid phase reaction is terminated by discharging the reaction product into the cooling mixer having a temperature of 20 ° C, from which it is later removed for the second melt-grafting step (Example 13).
  • MT / h a feed rate of 1.16 parts by mass per hour
  • L 42 D, temperatures in the range of 175 to 250 ° C, screw speed: 300 rev / min
  • Company Werner & Pfleiderer equipped with an underwater granulation (UWG) supplied.
  • UWG underwater granulation
  • Table 2 lists: Column 1: Example Number Column 2: Concentration of solid phase graft product used, specifying the corresponding Bspl.-Nr./Table 1, in parts by weight per hour [MT / h] Column 3: Type and concentration of LLDPE-HM w , HDPE-HM w or LLDPE / HDPE-Blend-HM w (PE-HM w ), in [MT / h] Column 4: Type and concentration of olefinic elastomer used in [MT / h] Column 5: measured at ZSK nozzle average melt temperature (T M ), in [° C] Column 6: Melt flow rate MFR (190 ° C / 5 kg), in g / 10 min [g / 10 '] Column 7: Grafted carboxylic acid content (CS ex ), in mass% [wt.%] Column 8: Peel strength, in [N / mm]
  • the grafted MSA or AS content CS ex ie the degree of grafting (also referred to as carboxylation or in MSA grafting as Malein michsgrad) has been determined by means of back-titration of not neutralized by the proportion of carboxylic acid (MSA or AS) potassium hydroxide solution as follows : After treatment for 6 h at 80 ° C of the residue obtained in boiling methanol of a 2 g graft product with a mixture of 100 ml of water-saturated xylene and 20 ml of 0.1 molar methanolic potassium hydroxide - after adding a few drops of a 1% methanolic phenolphthalein solution - Titration with 0.1 molar hydrochloric acid.
  • melt flow rates MFR (190 ° C / 5 kg application weight) have been determined according to ISO 1133.
  • Table 2 lists the melt-grafting parameters as well as the MFR and CS ex values obtained for the carboxylated ethylene (co) polymer systems consisting of the above-mentioned components.
  • peel strength a characteristic value for the peel strength ( peel strength ) is given as the property essential for the evaluation of the carboxylated ethylene copolymer blends of the present invention.
  • Table 2 Ex. Extruder driving characteristics No. Solid Phase Product Tab.1 [MT / h] PE-HM w [MT / h] Olefin-elastomer [MT / h] T M [° C] MFR (190/5) [g / 10 '] CS ex [% by weight] Peel strength [N / mm] 13 1,16 No.1 5.84 LLDPE-3 3.0 PER * 207 2.7 0.25 7.2 See 13A - 6.94 LLDPE-3 + 0.05 MSA + 0.01 DHBP 3.0 PER * 207 0.2 12:20 3.1 14 1,16 no.2 5.84 LLDPE-4 3.0 EOR * -1 215 5.5 0.26 7.0 15 1.4 No.
  • the granules obtained by means of UWG are extruded into 0.3 mm thick films, cut into strips 80 mm in length and 40 mm in width and placed between two Al strips of the same dimension. Subsequently, in a heating cabinet at 180 ° C, a tempering of AI / HV / AI composites, which are then measured after various storage times in the oven without additional weight and pressure.
  • the measurement is carried out after a storage time of 8 minutes on each of three cut (13.3 x 80) mm AI / HV / AI test strip.
  • the peel strengths given in Table 2 are the average values obtained from in each case four Al / HV / Al composites (and thus from a total of 12 sample individual values) for a tested adhesive.
  • the carboxylated ethylene polymer blends produced according to the invention are characterized by high adhesive strengths (peel strengths) with melt viscosities which are also well suited for use according to MFR (190 ° C / 5 kg) values between 1 and 7 g / 10 min.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Procedure for the manufacture of carboxylated ethylene polymer blends, in which in a 1st step, in a fluid mixing reactor, to 100 pbw of a particulate ethylene polymer—chosen from among ethylene homopolymers (HDPE, LDPE) and/or linear ethylene copolymers with 2 to ≰20 wt.-% polymerized-in C3-12-olefin units (LLDPE, EOP), with a melt-flow rate MFR (190° C./2.16 kg)≧20 g/10 min—are added 0.05-15 pbw of a α,β-ethylenically unsaturated mono and/or dicarboxylic acid or its anhydride (carboxyl monomer), or a monomer mixture containing at least one carboxyl monomer and 0.01-10 pbw of a radical initiator or initiator mixture, and graft-polymerizing at reaction temperatures of 30-120° C., over a reaction time of 5-120 min and subsequently, in a 2nd step, reacting a mixture continuously fed into a reaction extruder of 100 pbw of the modified ethylene polymer obtained in the 1st solid phase step, 150-4,000 pbw of an ethylene polymer or polymer blend with a melt flow rate MFR (190° C., 2.16 kg)<20 g/10 min, as well as 0-4,000 pbw of an olefinic elastomer, at temperatures of 160-260° C. and continuously removing the graft-modified ethylene polymer blend that has a degree of carboxylation of 0.05-1 wt.-%. The products obtained are especially suitable as adhesion promoters and/or adhesives for numerous substrates, preferably on and between metallic surfaces.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung carboxylierter Ethylenpolymerblends, zusammengesetzt aus mindestens zwei verschiedenen Ethylenhomo- und/oder -copolymeren, in zwei Stufen und ihre Verwendung als Haftvermittler in Kunststoff-Metall-Verbunden.The invention relates to a process for the preparation of carboxylated ethylene polymer blends composed of at least two different ethylene homopolymers and / or copolymers, in two stages and their use as adhesion promoters in plastic-metal composites.

Für zahlreiche Anwendungen, insbesondere als Verträglichkeits- bzw. Haftvermittler (Klebemittel), erfolgt der Einsatz von carboxylierten Olefinpolymeren auf Basis von Polyethylenen unterschiedlicher Dichte (LDPE, MDPE, HDPE), Ethylen/α,β-ethylenisch ungesättigten C3- bis C12-Olefin-Copolymeren (LLDPE, POE) oder auch von Propylenhomo- (HPP) sowie statistischen(Random) und heterophasigen Propylencopolymeren (RCP, HCP), Ethylen/Propylen-Copolymeren (EPC) oder Ethylen/Propylen/Dien-Terpolymeren (EPDM), die im Allgemeinen mittels reaktiver Extrusion bei hohen Temperaturen (150-300 °C) durch Pfropfung eines carboxylgruppenhaltigen Monomers, wie Acrylsäure, Fumarsäure und besonders Maleinsäureanhydrid, auf das olefinische Rückgratpolymer in Gegenwart eines Radikale bildenden peroxidischen Initiators hergestellt werden ( WO 91/18053 , US 4.174.358 , US 4.537.929 , US 4.684.576 , US 4.751.270 , US 4.927.888 , EP 0266221 B1 , EP 0287140 B1 , EP 0403109 A2 , EP 0467178 B1 , EP 0581360 B1 , EP 0696303 B1 , EP 0878510 B1 ).For numerous applications, in particular as compatibilizers or adhesion promoters (adhesives), the use of carboxylated olefin polymers based on polyethylenes of different densities (LDPE, MDPE, HDPE), ethylene / α, β-ethylenically unsaturated C 3 - to C 12 - Olefin copolymers (LLDPE, POE) or else propylene homo- (HPP) and also random (random) and heterophasic propylene copolymers (RCP, HCP), ethylene / propylene copolymers (EPC) or ethylene / propylene / diene terpolymers (EPDM), generally prepared by reactive extrusion at high temperatures (150-300 ° C) by grafting a carboxyl group-containing monomer such as acrylic acid, fumaric acid and especially maleic anhydride onto the olefinic backbone polymer in the presence of a radical-forming peroxidic initiator ( WO 91/18053 . US 4,174,358 . US 4,537,929 . US 4,684,576 . US 4,751,270 . US 4,927,888 . EP 0266221B1 . EP 0287140 B1 . EP 0403109 A2 . EP 0467178 B1 . EP 0581360 B1 . EP 0696303 B1 . EP 0878510 B1 ).

Während die bei niedrigeren Reaktionstemperaturen, d. h. unterhalb des Schmelzpunkts des olefinischen Rückgratpolymers (Pfropfsubstrats) durchgeführte Pfropfcarboxylierung, vorzugsweise -maleinierung, in einem Lösemittel auf Grund der technologisch sehr aufwendigen Polymer-Auflösung und vor allem der nach erfolgter Pfropfreaktion notwendigen Lösemittelabtrennung und -rückgewinnung sowie der erforderlichen Pfropfprodukt-Reinigung keine wirtschaftliche Alternative zur Schmelze-Pfropfung von Säure(anhydrid)monomeren ist, basiert die in fest-fluider partikulärer Polymerphase durchgeführte Carboxylierung von Olefinpolymeren auf einer unterhalb der Schmelz- bzw. der Erweichungstemperatur des Pfropfsubstrates durchgeführten wirtschaftlichen Technologie ( DD 275160 A3 , DD 275161 A3 , DD 300977 A7 , DE 4123972 A1 , DE 4342605 A1 , EP 0469693 B1 ).While at lower reaction temperatures, ie below the melting point of the olefinic backbone polymer (graft) graft carboxylation, preferably maleination, in a solvent due to the technologically very complex polymer dissolution and especially the necessary after the grafting solvent separation and recovery and the required Graft product purification is not an economical alternative to melt-grafting acid (anhydride) monomers, the carboxylation of olefin polymers carried out in solid-fluid particulate polymer phase is based on economical technology carried out below the melting or softening temperature of the graft substrate ( DD 275160 A3 . DD 275161 A3 . DD 300977 A7 . DE 4123972 A1 . DE 4342605 A1 . EP 0469693 B1 ).

Dafür besonders geeignete Rückgratpolymere sind teilkristalline Olefinpolymere, die in der sich zwischen ihrem Glas- und Schmelzpunkt ausbildenden amorphen Phase hohe Diffusionsgeschwindigkeiten für niedermolekulare Verbindungen wie Säure- bzw. Anhydridmonomere, eine der Voraussetzungen für ihre hohen Pfropfpolymerisationsgeschwindigkeiten, erlauben.Particularly suitable backbone polymers for this purpose are partially crystalline olefin polymers which, in the amorphous phase which forms between their glass and melting point, permit high diffusion rates for low molecular weight compounds such as acid or anhydride monomers, one of the prerequisites for their high graft polymerization rates.

Amorphe sowie niedrig-kristalline Olefinelastomere mit spezieller Morphologie sind als Polymerrückgrat für die freie radikalische Festphasen-Pfropfmodifizierung unter bestimmten Polymerisationsbedingungen auch verwendbar ( EP 0642538 B1 , EP 0805827 B1 ), ohne aber die für eine Verwendung als hochwirksame Haftvermittler, insbesondere für anspruchsvolle Metall/Kunststoff-Verbunde, erforderlichen Eigenschaften zu erreichen.Amorphous and low crystalline olefin elastomers with special morphology are also useful as polymer backbones for free radical solid phase graft modification under certain polymerization conditions ( EP 0642538 B1 . EP 0805827 B1 ), but without the properties required for use as a highly effective adhesion promoter, in particular for demanding metal / plastic composites.

Zu den möglichen Haftvermittlern zählen neben carboxylierten (maleinierten) Polyethylenen mit hoher Dichte (HDPE) oder verzweigten Polyethylenen mit niedriger Dichte (LDPE) vor allem auch carboxylierte lineare Ethylencopolymere mit niedriger Dichte, entweder mit einem niedrigen C3- bis C12-Olefin-Comonomeranteil unterhalb 15 Masse-% (LLDPE) oder mit höherem C3- bis C12-Olefin-Comonomeranteil (oberhalb 15 Masse-%, POE), insbesondere Ethylen/Octen(C8)-Copolymere (EOC), sowie auch aus überwiegend Propyleneinheiten bestehenden Random-Propylen/EthylenCopolymere, die zwecks ihrer Carboxylierung ausschließlich durch Schmelze-Pfropfung - bevorzugt unter Verwendung von MSA als Pfropfagens - hergestellt ( US 5.346.963 , US 6.384.139 B1 , US 6.331.592 B1 , US 6.884.850 B1 ; DE 198 41 303 A1 , WO 01/92357A1 , WO 98/42760 A1 , EP 0659784 B1 ) und als Klebemittel für verschiedene Einsatzfälle verwendet werden können ( EP 0696303 B1 , EP 0754731 B1 , EP 0878510 B1 ).Among the possible adhesion promoters, in addition to carboxylated (maleated) high density polyethylenes (HDPE) or branched low density polyethylenes (LDPEs), are primarily carboxylated linear low density ethylene copolymers, either with a low C 3 to C 12 olefin comonomer content below 15% by mass (LLDPE) or with a higher C 3 to C 12 olefin comonomer content (above 15% by mass, POE), in particular ethylene / octene (C 8 ) copolymers (EOC), as well as predominantly propylene units existing random-propylene / ethylene copolymers which, for the purpose of their carboxylation, are prepared exclusively by melt-grafting, preferably using MSA as grafting agent ( US 5,346,963 . US 6,384,139 B1 . US 6,331,592 B1 . US 6,884,850 B1 ; DE 198 41 303 A1 . WO 01 / 92357A1 . WO 98/42760 A1 . EP 0659784 B1 ) and can be used as adhesives for various applications ( EP 0696303 B1 . EP 0754731 B1 . EP 0878510 B1 ).

Für spezielle Einsatzgebiete werden auch schmelzecarboxylierte (-maleinierte) Ethylen/Vinylacetat- (EVA) oder Ethylen/(Meth)Acrylsäureester-Copolymere (E(M)AE) eingesetzt ( EP 0266994 A2 , EP 0647246 B1 , WO 93/01052 A1 ).For specific applications also melt-carboxylated (-maleinated) ethylene / vinyl acetate (EVA) or ethylene / (meth) acrylic acid ester copolymers (E (M) AE) are used ( EP 0266994 A2 . EP 0647246 B1 . WO 93/01052 A1 ).

Des Weiteren sind Klebharzmassen unter Verwendung von in Schmelze pfropfcarboxylierten Gemischen aus einem kristallinen Polyolefin, z. B. HDPE oder LLDPE, und einem amorphen oder gering kristallinem Olefincopolymer, z. B. Ethylen/Propylen-Kautschuk (EPM) bekannt ( EP 0501762 B1 ).Further, adhesive resin compositions using melt graft carboxylated mixtures of a crystalline polyolefin, for. HDPE or LLDPE, and an amorphous or low crystalline olefin copolymer, e.g. B. ethylene / propylene rubber (EPM) known ( EP 0501762 B1 ).

Der Nachteil der bekannten schmelzegepfropften Ethylenhomo- und -copolymere sowie pfropfmodifizierten olefinischen Elastomere besteht in ihren hohen Molmassen, die sich während der Pfropfreaktion bilden und die sich besonders bei ihrer Verwendung als Klebemittel negativ auswirken, sowie den insgesamt kostenintensiven Maßnahmen für die Entfernung von Restmonomer(en).The disadvantage of the known melt-grafted ethylene homo- and copolymers and graft-modified olefinic elastomers is their high molecular weights, which are formed during the grafting reaction and which have a negative effect especially when used as adhesives, and the overall costly measures for the removal of residual monomer (s ).

Die Aufgabe der vorliegenden Erfindung bestand darin - unter Vermeidung der beschriebenen Nachteile - ein Verfahren zur Herstellung eines Haftvermittlers (Klebemittels) auf Basis der Carboxylierung von Polyethylenen (HDPE, LDPE) und/oder Ethylen/ α,β-ethylenisch ungesättigten C3- bis C12-Olefin-Copolymeren (EPC, LLDPE, POE) zu entwickeln.The object of the present invention was - while avoiding the disadvantages described - a process for the preparation of a coupling agent (adhesive) based on the carboxylation of polyethylenes (HDPE, LDPE) and / or ethylene / α, β-ethylenically unsaturated C 3 - to C To develop 12- olefin copolymers (EPC, LLDPE, POE).

Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung carboxylierter Ethylenpolymerblends in zwei Stufen, wonach in einer 1. Stufe in einem Fluidmischreaktor auf 100 Masseteile fest-fluides partikuläres Ethylenpolymer mit MFR (190 °C/2,16 kg Auflagegewicht) ≥ 20 g/10 min, ausgewählt unter Ethylenhomopolymeren und/oder linearen Ethylencopolymeren der Zusammensetzung ≥ 80 bis 98 Masse-% Ethylen-/2 bis ≤ 20 Masse-% C3- bis C12-Olefineinheiten, 0,05 bis 15 Masseteile einer α,β-ethylenisch ungesättigten Mono- und/oder Dicarbonsäure bzw. deren Anhydrid (Carboxylmonomer) oder einer mindestens ein Carboxylmonomer enthaltenden Monomermischung sowie 0,01 bis 10 Masseteile eines freie Radikale bildenden Initiators mit einer 1-Stunde-Halbwertszeittemperatur (THW/1h) zwischen 50 und 200 °C oder entsprechenden Initiatorgemischs hinzugefügt und bei Reaktionstemperaturen zwischen 30 und 120°C über eine Reaktionszeit zwischen 5 und 120 min pfropfpolymerisiert
und anschließend in einer 2. Stufe
100 Masseteile des in der 1. Festphasenstufe erhaltenen modifizierten Ethylenpolymers zusammen mit 150 bis 4000 Masseteilen eines unmodifizierten Ethylenpolymers oder -polymerblends mit einer Schmelzflussrate MFR (190 °C/2,16 kg Auflagegewicht) < 20 g/10 min, ausgewählt unter Ethylenhomopolymeren oder Ethylencopolymeren der Zusammensetzung ≥ 85 bis 98 Masse-% Ethylen-/2 bis ≤ 15 Masse-% C3- bis C12-Olefineinheiten oder aus LLDPE und HDPE bestehenden Compounds oder Reaktorblends, sowie 0 bis 4000 Masseteilen eines olefinischen Elastomers der Zusammensetzung 10 bis 100 Masse-% Propylen- und 0 bis 90 Masse-% einpolymerisierten Ethylen- und/oder C4- bis C12-Olefin- und/oder Dieneinheiten oder auf Basis eines Ethylencopolymers mit 10 bis 80 Masse-% einpolymerisierten Vinylacetat- oder (Meth)Acrylsäureestereinheiten über gravimetrische Dosiereinrichtungen einem Reaktionsextruder kontinuierlich zugeführt und bei Reaktionstemperaturen zwischen 160 und 260 °C umgesetzt werden und am Reaktorende das einen Carboxylierungsgrad zwischen 0,05 und 1 Masse-% besitzende pfropfmodifizierte Olefinpolymerblend kontinuierlich ausgetragen wird.The present invention is a process for preparing carboxylated ethylene polymer blends in two stages, wherein in a first stage in a fluid mixing reactor to 100 parts by mass solid-fluid particulate ethylene polymer with MFR (190 ° C / 2.16 kg support weight) ≥ 20 g / 10 min, selected from ethylene homopolymers and / or linear ethylene copolymers of composition ≥ 80 to 98% by mass of ethylene / 2 to ≤ 20% by mass of C 3 to C 12 olefin units, 0.05 to 15 parts by mass of an α, β-ethylenic unsaturated mono- and / or dicarboxylic acid or its anhydride (carboxyl monomer) or a monomer mixture containing at least one carboxyl monomer and 0.01 to 10 parts by weight of a free radical initiator having a 1-hour half-life temperature (T HW / 1h ) between 50 and 200 ° C or corresponding initiator mixture added and graft polymerized at reaction temperatures between 30 and 120 ° C over a reaction time between 5 and 120 min
and then in a 2nd stage
100 parts by mass of the modified solid polymer obtained in the 1st solid phase step together with 150 to 4000 parts by mass of an unmodified ethylene polymer or polymer blend having a melt flow rate MFR (190 ° C / 2.16 kg load) <20 g / 10 min, selected from ethylene homopolymers or ethylene copolymers of the composition ≥ 85 to 98% by mass of ethylene / 2 to ≤ 15% by mass of C 3 to C 12 olefin units or of LLDPE and HDPE compounds or reactor blends, and 0 to 4000 parts by mass of an olefinic elastomer of the composition 10 to 100 Mass% of propylene and 0 to 90% by mass of copolymerized ethylene and / or C 4 to C 12 olefin and / or diene units or based on an ethylene copolymer with 10 to 80% by mass of copolymerized vinyl acetate or (meth) Acrylic ester units via gravimetric dosing continuously fed to a reaction extruder and reacted at reaction temperatures between 160 and 260 ° C and at the reactor end, a degree of carboxylation between 0.05 and 1 mass% possessing graft-modified Olefinpolymerblend is continuously discharged.

Während für den erfindungsgemäßen Carboxylierungsprozess in der 1. Stufe leichter fließende Ethylenpolymere mit MFR (190 °C/2,16 kg) ≥ 20 g/10 min, d. h. solche mit niedrigerer Molmasse Mw (NMw), ausgewählt unter linearen Polyethylenen mit hoher Dichte (HDPE-NMw) oder verzweigten Polyethylenen mit niedriger Dichte (LDPE-NMw) oder linearen Ethylencopolymeren mit 2 bis maximal 20 Masse-% C3- bis C12-Olefineinheiten (LLDPE-NMw, EOP-NMw), eingesetzt werden, wird für die nachfolgende Schmelzepfropfstufe zusammen mit dem in der Festphasenstufe modifizierten Ethylenpolymer ein unmodifiziertes geringer fließendes Ethylenhomo- und/oder -copolymer mit MFR (190 °C/ 2,16 kg) < 20 g/10 min, d. h. ein Ethylenpolymer mit höherer Molmasse Mw (HMw) entsprechend HDPE-HMw, LDPE-HMW, LLDPE-HMw oder auch einem HDPE/LLDPE-Blend-HMw, verwendet.While for the carboxylation process according to the invention in the 1st stage more easily flowing ethylene polymers with MFR (190 ° C / 2.16 kg) ≥ 20 g / 10 min, ie those with lower molecular weight M w (NM w ) selected from linear polyethylenes with high Density (HDPE-NM w ) or branched low density polyethylenes (LDPE-NM w ) or linear ethylene copolymers containing from 2 to a maximum of 20% by mass of C 3 to C 12 olefin units (LLDPE-NM w , EOP-NM w ), For example, for the subsequent melt grafting step, along with the solid phase modified ethylene polymer, is an unmodified low-flow ethylene homo- and / or copolymer having MFR (190 ° C / 2.16 kg) <20 g / 10 min, ie an ethylene polymer higher molecular weight M w (HM w ) corresponding to HDPE-HM w , LDPE-HM W , LLDPE-HM w or even a HDPE / LLDPE blend HM w used.

Darüber hinaus wird zumeist ein olefinisches Elastomer, ausgewählt unter den elastomeren Polypropylenen (ELPP) oder statistischen Propylencopolymeren mit 5 bis 50 Masse-% Ethylen- und/oder α,β-ethylenisch ungesättigten C4- bis C8-Olefin- und/oder Dieneinheiten, vorzugsweise 10 bis 25 Masse-% Ethyleneinheiten (PER), oder Ethylencopolymeren mit ≥ 20 Masse-% α,β-ethylenisch ungesättigten C3- bis C12-Olefineinheiten (EOR), vorzugsweise Propylen-, Buten-, Hexen- bzw. Methylpenten- oder Octeneinheiten, besonders bevorzugt mit 25 bis 50 Masse-% Propylen-(EPR*), Buten-1- (EBR*) oder Octen-1-Einheiten (EOR*), oder ein Ethylen/Vinylacetat- (EVA) oder ein Ethylen/(Meth)Acrylsäureester-Copolymer (E(M)AE), vorzugsweise ein Ethylencopolymer mit ≥ 15 Masse-% einpolymerisierten Butylacrylateinheiten (EBA), eingesetzt.In addition, an olefinic elastomer selected from among the elastomeric polypropylenes (ELPP) or random propylene copolymers containing from 5 to 50% by weight of ethylene and / or α, β-ethylenically unsaturated C 4 to C 8 olefin and / or diene units is most commonly used , preferably 10 to 25% by mass of ethylene units (PER), or ethylene copolymers having ≥20% by mass of α, β-ethylenically unsaturated C 3 to C 12 olefin units (EOR), preferably propylene, butene, hexene or Methyl pentene or octene units, more preferably with 25 to 50 mass% of propylene (EPR *), butene-1 (EBR *) or octene-1 units (EOR *), or an ethylene / vinyl acetate (EVA) or an ethylene / (meth) acrylic acid ester copolymer (E (M) AE), preferably an ethylene copolymer with ≥ 15% by mass of copolymerized butyl acrylate units (EBA).

Für verschiedene Anwendungen als Klebemittel, vor allem wenn nicht unbedingt Haftfestigkeiten > 3 N/mm notwendig sind, kann der Zusatz des olefinischen Elastomers entfallen (spezielle Ausführungsform auf Basis von 0 Masseteilen Elastomer).For various applications as adhesives, especially if not necessarily adhesive strengths> 3 N / mm are necessary, the addition of the olefinic elastomer can be omitted (special embodiment based on 0 parts by mass of elastomer).

Im Unterschied zu den bekanntlich bei hohem Druck und hoher Temperatur mittels radikalischer Initiatoren hergestellten verzweigten Polyethylenen mit niedriger Dichte zwischen 0,910 und 0,940 g/cm3 (LDPE) werden die linearen Polyethylene mit hoher Dichte zwischen 0,940 und 0,965 g/cm3 (HDPE) und linearen Ethylen/< 15 Masse-% C3- bis C12-Olefin-Copolymere mit niedriger Dichte < 0,940 g/cm3 (LLDPE) im Allgemeinen mittels bekannter Technologien der koordinativen Katalyse unter Verwendung der Katalysatoren des Ziegler- bzw. Ziegler-Natta- oder Phillips-Typs erzeugt.In contrast to the low-density branched polyethylenes with low density between 0.910 and 0.940 g / cm 3 (LDPE), which are known to be produced at high pressure and high temperature by means of free-radical initiators, the linear high density polyethylenes are between 0.940 and 0.965 g / cm 3 (HDPE) and linear ethylene / <15 mass% of low density C 3 to C 12 olefin copolymers <0.940 g / cm 3 (LLDPE), generally by known coordinate coordination techniques using Ziegler and Ziegler-Natta catalysts, respectively - or Phillips-type generated.

Dem gegenüber werden die erfindungsgemäß einsetzbaren Ethylencopolymere mit hohem C3- bis C12-Olefin-Anteil ≥ 15 Masse-% (EOP, EOR) und die aus überwiegend Propyleneinheiten zusammengesetzten Olefinelastomere, wie besonders PER, sowie elastomeren Polypropylene (ELPP) bekanntermaßen unter Verwendung spezieller Metallocen-Katalysatorsysteme hergestellt.On the other hand, the ethylene copolymers having high C 3 to C 12 olefin content ≥15% by mass (EOP, EOR) and the olefin elastomers composed mainly of propylene units, such as especially PER, and elastomeric polypropylenes (ELPP) are known to be used made of special metallocene catalyst systems.

Die Verwendung von aus mindestens zwei unterschiedlichen Ethylen(co)polymeren bestehenden Blends, insbesondere für die Schmelzepfropfstufe, in Form von Compounds oder auch Reaktorblends, ist eine geeignete Ausführungsform des erfindungsgemäßen Verfahrens, wonach in der 2. Stufe ein Blend aus 10-90 Masse-% LDPE oder LLDPE und 90-10 Masse-% HDPE, vorzugsweise aus 20-80 Masse-% LLDPE und 80-20 Masse-% HDPE, mit einem MFR (190 °C/2,16 kg) < 20 g/10 min, dem Reaktor, vorzugsweise einem Doppelschneckenkneter (DSK), eingesetzt wird.The use of blends consisting of at least two different ethylene (co) polymers, in particular for the melt-grafting stage, in the form of compounds or reactor blends, is a suitable embodiment of the process according to the invention, according to which a blend of 10-90% by weight % LDPE or LLDPE and 90-10% by mass HDPE, preferably from 20-80% by mass LLDPE and 80-20% by mass HDPE, with MFR (190 ° C / 2.16 kg) <20 g / 10 min , the reactor, preferably a twin-screw kneader (DSK), is used.

Das Carboxylmonomer, vorzugsweise Maleinsäureanhydrid (MSA) und/oder Acrylsäure (AS), kann auch als Mischung mit einem Comonomer aus der Gruppe der Vinylaromate, vorzugsweise Styrol, und/oder der C1- bis C12-Alkylester der Acryl- oder Methacrylsäure, vorzugsweise Methylmethacrylat (MMA) oder Methyl- (MA) oder Ethyl- (EA) oder Butylacrylat (BA), entsprechend Zusammensetzungen 99-20 Masse-% Carboxyl- und 1-80 Masse-% Comonomer, vorzugsweise 90-50 Masse-% MSA und/oder AS und 10-50 Masse-% Styrol, in der Festphasenstufe eingesetzt werden.The carboxyl monomer, preferably maleic anhydride (MSA) and / or acrylic acid (AS), can also be used as a mixture with a comonomer from the group of vinyl aromatics, preferably styrene, and / or the C 1 to C 12 alkyl esters of acrylic or methacrylic acid, preferably methyl methacrylate (MMA) or methyl (MA) or Ethyl (EA) or butyl acrylate (BA), corresponding compositions 99-20% by mass of carboxyl and 1-80% by mass of comonomer, preferably 90-50% by mass of MSA and / or AS and 10-50% by mass of styrene , be used in the solid phase stage.

Die radikalisch initiierte zweistufige Pfropfung wird zwecks Erreichung ausreichender Carboxylierungsgrade sowie einer gleichmäßigen Pfropfung vorteilhaft unter Verwendung eines Radikalbildners oder vorzugsweise einer aus mindestens zwei verschiedenen Radikalbildnern bestehenden Mischung unter Verwendung organischer Peroxide mit Halbwertstemperaturen nach einer Stunde THW/1h zwischen 50 und 200 °C bzw. nach einer Minute THW/1min zwischen 85 und 250 °C (gemessen in 0,1 molarer Monochlorbenzol-Lösung), in einer auf die gesamte Ethylenpolymer-Pfropfsubstratmenge bezogenen Konzentration zwischen 0,001 und 5 Masse-%, vorzugsweise zwischen 0,02 und 2 Masse-%, durchgeführt.The radically initiated two-stage grafting is advantageously carried out using a free-radical generator or preferably consisting of at least two different radical formers using organic peroxides having half-life temperatures after one hour T HW / 1h between 50 and 200 ° C or to achieve uniform grafting. after one minute T HW / 1min between 85 and 250 ° C (measured in 0.1 molar monochlorobenzene solution) in a concentration based on the total ethylene polymer graft substrate amount between 0.001 and 5 mass%, preferably between 0.02 and 2 Mass%, performed.

Ausgewählte Beispiele für verwendbare Radikalbildner sind Dialkylperoxidicarbonate mit einer 1-Stunde-Halbwertszeittemperatur (THW/1h) zwischen 55 und 66 °C, vorzugsweise Dibutylperoxidicarbonat (DBPOC) und Dicetylperoxidicarbonat (DCPOC) mit THW/1h von 65 °C, Dilauroylperoxid (DLPO) mit THW/1h von 80 °C, Dibenzoylperoxid (DBPO) mit THW/1h von 91°C, tert.-Butylperoxy-2-ethylhexanoat (TBPEH) mit THW/1h von 91 °C, tert.-Butylperoxy-isobutyrat (TBPIB) mit THW/1h von 98 °C, 1,1-Di-(tert.-butylperoxy)-cyclohexan (DTBPC) mit THW/1h von 113 °C, tert.-Butylperbenzoat (TBPB) mit THW/1h von 122 °C, Dicumylperoxid (DCP) mit THW/1h von 132 °C, 2,5-Dimethyl-2,5-di(tert.-butylperoxy)-hexan (DHBP) mit THW/1h von 134 °C, 2,5-Dimethyl-2,5-di(tert.-butylperoxy)hexin-(3) (DYBP) mit THW/1h von 141 °C, Di-tert.-butylperoxid (TBP) mit THW/1h von 141 °C, Cumolhydroperoxid (CHP) mit THW/1h von 166 °C und tert.-Butylhydroperoxid (TBHP) mit THW/1h von 185 °C.Selected examples of useful free radical generators are dialkyl peroxydicarbonates having a 1 hour half life temperature (T HW / 1h ) between 55 and 66 ° C, preferably dibutyl peroxydicarbonate (DBPOC) and dicetyl peroxydicarbonate (DCPOC) with T HW / 1h of 65 ° C, dilauroyl peroxide (DLPO ) with T HW / 1h of 80 ° C, dibenzoyl peroxide (DBPO) with T HW / 1h of 91 ° C, tert-butyl peroxy-2-ethylhexanoate (TBPEH) with T HW / 1h of 91 ° C, tert-butyl peroxy -isobutyrate (TBPIB) with T HW / 1h of 98 ° C, 1,1-di- (tert-butylperoxy) -cyclohexane (DTBPC) with T HW / 1h of 113 ° C, tert-butyl perbenzoate (TBPB) with T HW / 1h of 122 ° C, dicumyl peroxide (DCP) with T HW / 1h of 132 ° C, 2,5-dimethyl-2,5-di (tert-butylperoxy) -hexane (DHBP) with T HW / 1h of 134 ° C, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne (3) (DYBP) with T HW / 1h of 141 ° C, di-tert-butyl peroxide (TBP) with T HW / 1h of 141 ° C, cumene hydroperoxide (CHP) with T HW / 1h of 166 ° C and tert-butyl hydroperoxide (TBHP) with T HW / 1h of 185 ° C.

Eine bevorzugte Ausführungsform des Verfahrens zur Herstellung carboxylierter Ethylenpolymere bzw. Ethylencopolymerblends besteht darin, dass in der 1. Stufe auf 100 Masseteile partikuläres Ethylenpolymer mit MFR (190 °C/2,16 kg) zwischen 20 und 1000 g/10 min, ausgewählt unter einem Ethylenhomopolymer (HDPE-NMw, LDPE-NMw) und/oder linearem Ethylencopolymer der Zusammensetzung ≥ 90 bis 98 Masse-% Ethylen-/2 bis ≤ 10 Masse-% C3- bis C8-Olefineinheiten (LLDPE*-NMw), 0,2 bis 12 Masseteile MSA, allein oder als Monomermischung mit 0,02 bis 6 Masseteilen Styrol, unter Zusatz von 0,05 bis 5 Masseteilen einer aus mindestens zwei radikalbildenden Initiatoren mit unterschiedlichen 1-Stunde-Halbwertszeittemperaturen (THW/1h) zwischen 50 und 120 °C sowie zwischen 120 und 180 °C bestehenden Mischung bei Reaktionstemperaturen zwischen 50 und 100 °C über eine Reaktionszeit zwischen 8 und 80 min pfropfpolymerisiert
und anschließend in der 2. Stufe
eine Mischung aus 100 Masseteilen des in der 1. Festphasenstufe erhaltenen modifizierten Ethylen(co)polymers, 180-3600 Masseteilen eines unmodifizierten Ethylenpolymers oder -polymerblends mit einem MFR (190 °C/2,16 kg) zwischen 0,1 und 20 g/10 min, ausgewählt unter Ethylenhomopolymeren (HDPE-HMw, LDPE-HMw) oder Ethylencopolymeren der Zusammensetzung ≥ 90 bis 98 Masse-% Ethylen-/2 bis ≤ 10 Masse-% C3- bis C8-Olefineinheiten (LLDPE*-HMw) oder HDPE/LLDPE-Blends-HMw, sowie 100-3000 Masseteilen eines aus 50 bis 75 Masse-% Ethylen- und 25 bis 50 Masse-% C3- bis C8-Olefineinheiten (EOR) oder aus 70 bis 100 Masse-% Propylen- und 0 bis 30 Masse-% Ethyleneinheiten bestehenden Elastomers (ELPP, PER), das mindestens ein bekanntes Stabilisationsmittel und/ oder Antioxydans enthält, kontinuierlich einem Extruder zugeführt, bei Massetemperaturen zwischen 170 und 250 °C umgesetzt und aus der Extruderdüse ein pfropfmodifiziertes Olefinpolymerblend mit einem Carboxylierungsgrad zwischen 0,1 und 0,6 Masse-% kontinuierlich ausgetragen wird.A preferred embodiment of the process for producing carboxylated ethylene copolymers or ethylene copolymer blends is that in the first stage to 100 parts by weight of particulate ethylene polymer with MFR (190 ° C / 2.16 kg) between 20 and 1000 g / 10 min, selected from a Ethylene homopolymer (HDPE-NM w , LDPE-NM w ) and / or linear ethylene copolymer of composition ≥ 90 to 98% by mass ethylene / 2 to ≤ 10% by mass C 3 to C 8 olefin units (LLDPE * -NM w ), 0.2 to 12 parts by weight of MSA, alone or as a monomer mixture with 0.02 to 6 parts by weight of styrene, with the addition of 0.05 to 5 parts by weight of one of at least two radical-forming Initiators with different 1-hour half-life temperatures (T HW / 1h ) between 50 and 120 ° C and between 120 and 180 ° C existing mixture at reaction temperatures between 50 and 100 ° C for a reaction time between 8 and 80 min graft polymerized
and then in the 2nd stage
a blend of 100 parts by weight of the modified solid state (co) polymer obtained in the 1st solid state step, 180-3600 parts by weight of an unmodified ethylene polymer or polymer blend having an MFR (190 ° C / 2.16 kg) between 0.1 and 20 g / 10 min, selected from ethylene homopolymers (HDPE-HM w , LDPE-HM w ) or ethylene copolymers of composition ≥ 90 to 98% by mass ethylene / 2 to ≤ 10% by mass C 3 - to C 8 -olefin units (LLDPE * - HM w ) or HDPE / LLDPE blends HM w , and 100-3000 parts by weight of a from 50 to 75% by mass of ethylene and 25 to 50% by mass of C 3 to C 8 olefin units (EOR) or from 70 to 100% by mass of propylene and 0 to 30% by mass ethylene units of existing elastomer (ELPP, PER) containing at least one known stabilizer and / or antioxidant, continuously fed to an extruder, reacted at melt temperatures between 170 and 250 ° C and from the Extruder die a graft modified olefin polymer blend with a Carboxylierungsgra d between 0.1 and 0.6 mass% is discharged continuously.

Entsprechend dieser bevorzugten Verfahrensvariante wird mit dem olefinischen Elastomer das für das gesamte carboxylierte Ethylenpolymerblend benötigte Stabilisationsmittel/Antioxydans, in bzw. auf dem es mittels separater Mischtechnologie dispergiert worden ist, zugeführt.According to this preferred variant of the method, the olefinic elastomer is used for the stabilizer / antioxidant required for the entire carboxylated ethylene polymer blend, in or on which it has been dispersed by means of a separate mixing technology.

Als Stabilisationsmittel und/oder Antioxydantien sind die für olefinische Polymere und Elastomere bekannten Substanzen, insbesondere primäre Antioxydantien auf Basis sterisch gehinderter Phenolverbindungen, in einer auf 100 Masseteile Olefinelastomer bezogenen Menge von 0,01 bis 5 Masseteilen, vorzugsweise von 0,1 bis 2 Masseteilen, einsetzbar. Auch Kombinationen aus jeweils mindestens einem primären und einem sekundären Antioxydans, wie z. B. Systeme aus einer sterisch gehinderten Phenol- und einer Phosphitverbindung, können verwendet werden.Stabilizing agents and / or antioxidants are the substances known for olefinic polymers and elastomers, especially primary antioxidants based on sterically hindered phenol compounds, in an amount of from 0.01 to 5 parts by weight, preferably from 0.1 to 2 parts by weight, based on 100 parts by weight of olefin elastomer. used. Also, combinations of at least one primary and one secondary antioxidant, such as. B. systems of a sterically hindered phenol and a phosphite compound can be used.

Bevorzugt können die pfropfmodifizierten Ethylenpolymerblends mit einem Carboxylierungsgrad zwischen 0,05 und 1 Masse-%, vorzugsweise zwischen 0,1 und 0,6 Masse-%, als Haftvermittler und/oder Klebemittel für verschiedene Unterlagen, vorzugsweise auf und zwischen metallischen Oberflächen, verwendet werden.Preferably, the graft-modified ethylene polymer blends having a degree of carboxylation between 0.05 and 1% by weight, preferably between 0.1 and 0.6% by weight, can be used as adhesion promoters and / or adhesives for various substrates, preferably on and between metallic surfaces ,

Das erfindungsgemäße Verfahren wird durch nachfolgende Beispiele erläutert, ohne darauf beschränkt zu sein.The process according to the invention is illustrated by the following examples, without being limited thereto.

1. Stufe (Festphasenpfropfstufe)1st stage (solid phase grafting stage) Beispiel 1example 1

In einen temperierbaren, mit einem stufenlos regelbaren Rührer ausgerüsteten Fluidmischreaktor der Firma Reimelt Henschel werden 96,6 Masseteile eines pulverigen LLDPE mit einer Dichte von 0,920 g/cm3, einer Schmelzflussrate MFR (190 °C/2,16 kg) von 47 g/10 min und einem mittleren Teilchendurchmesser dT von 0,21 mm (LLDPE-1) zusammen mit 0,16 Masseteilen Dicetylperoxidicarbonat (DCPOC), 0,47 Masseteilen 2,5-Dimethyl-2,5-di(tert.-butylperoxy)-hexan (DHBP) und 2,69 Masseteilen MSA bei einer Reaktorinnentemperatur von 20 °C vorgelegt. Danach wird in Stickstoff-Atmosphäre bei einer Rührgeschwindigkeit von 400 min-1 unter gleichzeitiger Temperaturerhöhung mit einer Aufheizgeschwindigkeit von 1,2 °C/min die Reaktionsmischung dispergiert und bei Erreichung der Endreaktionstemperatur TR1 von 70 °C über eine Zeit tR1 von 60 min auf TR1 gehalten.96.6 parts by weight of a powdery LLDPE having a density of 0.920 g / cm 3 , a melt flow rate MFR (190 ° C./2.16 kg) of 47 g / m, are prepared in a temperature-controllable fluid mixer reactor from Reimelt Henschel equipped with a continuously variable stirrer. 10 min and an average particle diameter d T of 0.21 mm (LLDPE-1) together with 0.16 parts by weight of dicetyl (DCPOC), 0.47 mass parts of 2,5-dimethyl-2,5-di (tert-butylperoxy) Hexane (DHBP) and 2.69 parts by weight of MSA presented at an internal reactor temperature of 20 ° C. Thereafter, the reaction mixture is dispersed in a nitrogen atmosphere at a stirring speed of 400 min -1 with simultaneous increase in temperature at a heating rate of 1.2 ° C / min and upon reaching the final reaction temperature T R1 of 70 ° C over a time t R1 of 60 min held on T R1 .

Die Festphasenreaktion wird beendet, indem das Reaktionsprodukt in den eine Temperatur von 20 °C aufweisenden Kühlmischer abgelassen wird, aus dem es für die 2. Schmelzepfropfstufe später entnommen wird (Beispiel 13).The solid phase reaction is terminated by discharging the reaction product into the cooling mixer having a temperature of 20 ° C, from which it is later removed for the second melt-grafting step (Example 13).

Beispiele 2 bis 12Examples 2 to 12

Entsprechend der in Beispiel 1 beschriebenen Prozessführung werden unter Verwendung nachfolgender pulverförmiger Ethylenpolymer-Pfropfsubstrate

  • LLDPE-1: Dichte = 0,920 g/cm3, MFR (190°C/2,16 kg) = 47 g/10 min
  • LLDPE-2: Dichte = 0,915 g/cm3, MFR (190°C/2,16 kg) = 25 g/10 min HDPE-1: Dichte = 0,958 g/cm3, MFR (190°C/2,16 kg) = 38 g/10 min Ethylen/Octen-Copolymer mit C8-Anteil von 16 Ma.-% (EOP*):
    Dichte = 0,913 g/cm3, MFR (190°C/2,16 kg) = 30 g/10 min mittels Zusatz von MSA oder AS bzw. einer MSA/Styrol(S)- oder AS/S-Mischung sowie einer Kombination aus zwei peroxidischen Initiatoren in der Festphase weitere pfropfmodifizierte Ethylen(co)polymere hergestellt.
According to the process procedure described in Example 1, using the following powdery ethylene polymer graft substrates
  • LLDPE-1: Density = 0.920 g / cm 3 , MFR (190 ° C / 2.16 kg) = 47 g / 10 min
  • LLDPE-2: Density = 0.915 g / cm 3 , MFR (190 ° C / 2.16 kg) = 25 g / 10 min HDPE-1: Density = 0.958 g / cm 3 , MFR (190 ° C / 2.16 kg) = 38 g / 10 min ethylene / octene copolymer with C 8 content of 16% by mass (EOP *):
    Density = 0.913 g / cm 3 , MFR (190 ° C / 2.16 kg) = 30 g / 10 min by the addition of MSA or AS or an MSA / styrene (S) - or AS / S mixture and a combination of two peroxide initiators in the solid phase further graft-modified ethylene (co) polymers produced.

Als Initiatoren sind DHBP, DCPOC und DLPO eingesetzt worden.As initiators DHBP, DCPOC and DLPO have been used.

Unter Beibehaltung des gemäß Beispiel 1 angewandten Chargier- und Aufheizregimes sind als wesentliche Parameter die Reaktionsendtemperatur TR1 und die für TR1 relevante Reaktionszeit tR1 sowie das Monomer/Initiator-Verhältnis entsprechend den in Tabelle 1 angegebenen Beispielen variiert worden. Tabelle 1 Bspl. Nr. Olefinpolymer [Ma.-%] Initiator [Ma.-%] Carboxyl-monomer [Ma.-%] Comonomer [Ma.-%] tR1 [min] TR1 [°C] 1 96,6 LLDPE-1 0,16 DCPOC 2,69 MSA - 60 70 0,47 DHBP 2 96,64 LLDPE-2 0,20 DLPO 2,69 MSA - 60 85 0,47 DHBP 3 96,7 LLDPE-2 0,12 DCPOC 2,69 MSA - 55 70 0,47 DHBP 4 96,68 HDPE-1 0,16 DLPO 2,69 MSA - 55 85 0,47 DHBP 5 95,3 HDPE-1 0,12 DCPOC 2,69 MSA 1,35 S 60 68 0,47 DHBP 6 95,3 LLDPE-1 0,17 DLPO 2,69 MSA 1,35 S 50 90 0,47 DHBP 7 88,5 LLDPE-2 0,22 DLPO 9,6 MSA - 65 85 1,65 DHBP 8 88,55 HDPE-1 0,20 DCPOC 9,6 MSA - 60 70 1,65 DHBP 9 92,1 LLDPE-1 0,18 DCPOC 5,4 AS 1,5 S 50 75 0.82 DHBP 10 93,5 LLDPE-1 0,18 DCPOC 5,4 MSA - 60 70 0.92 DHBP 11 96,64 EOP* 0,20 DLPO 2,69 MSA - 60 85 0,47 DHBP 12. 94,4 EOP* 0,15 DCPOC 3,6 AS 1,2 S 60 70 0,65 DHBP Tabelle 1 enthält die für die 1. Stufe wichtigen Verfahrensparameter:

  • Beispiel-Nummer (Spalte 1)
  • eingesetztes Ethylenpolymer (Pfropfsubstrat), in Masse-% (Ma.-%) (Spalte 2)
  • Art und Konzentration der verwendeten Initiatoren, in Ma.-% (Spalte 3)
  • MSA oder AS mit Konzentrationsangabe, in Ma.-% (Spalte 4)
  • Styrol (S) mit Konzentrationsangabe, in Ma.-% (Spalte 5)
  • Reaktionszeiten (tR1), in min (Spalte 6)
  • Reaktionsendtemperaturen (TR1), in °C (Spalte 7)
While maintaining the charging and Aufheizregimes Example 1 are applied in accordance with the essential parameters the final reaction temperature T R1 and T for the relevant R1 reaction time t and R1 been varied according to the specified in Table 1 examples, the monomer / initiator ratio. <u> Table 1 </ u> Ex. No. Olefin polymer [% by mass] Initiator [% by weight] Carboxyl monomer [% by mass] Comonomer [% by mass] t R1 [min] T R1 [° C] 1 96.6 LLDPE-1 0.16 DCPOC 2.69 MSA - 60 70 0.47 DHBP 2 96.64 LLDPE-2 0.20 DLPO 2.69 MSA - 60 85 0.47 DHBP 3 96.7 LLDPE-2 0.12 DCPOC 2.69 MSA - 55 70 0.47 DHBP 4 96.68 HDPE-1 0.16 DLPO 2.69 MSA - 55 85 0.47 DHBP 5 95.3 HDPE-1 0.12 DCPOC 2.69 MSA 1.35 p 60 68 0.47 DHBP 6 95.3 LLDPE-1 0.17 DLPO 2.69 MSA 1.35 p 50 90 0.47 DHBP 7 88.5 LLDPE-2 0.22 DLPO 9.6 MSA - 65 85 1.65 DHBP 8th 88.55 HDPE-1 0.20 DCPOC 9.6 MSA - 60 70 1.65 DHBP 9 92.1 LLDPE-1 0.18 DCPOC 5.4 AS 1.5 s 50 75 0.82 DHBP 10 93.5 LLDPE-1 0.18 DCPOC 5.4 MSA - 60 70 0.92 DHBP 11 96.64 EOP * 0.20 DLPO 2.69 MSA - 60 85 0.47 DHBP 12th 94.4 EOP * 0.15 DCPOC 3.6 AS 1,2s 60 70 0.65 DHBP Table 1 contains the process parameters important for the 1st stage:
  • Example number (column 1)
  • Ethylene polymer (graft substrate) used, in% by mass (wt .-%) (column 2)
  • Type and concentration of the initiators used, in% by mass (column 3)
  • MSA or AS with concentration, in% by mass (column 4)
  • Styrene (S) with concentration, in% by mass (column 5)
  • Reaction times (t R1 ), in min (column 6)
  • Reaction end temperatures (T R1 ), in ° C (column 7)

2. Stufe Schmelzepfropfstufe)2nd stage melt-grafting stage) Beispiele 13 bis 27Examples 13 to 27

Das in der ersten Stufe erhaltene pulverige Festphasenprodukt Bspl.-Nr. 1 wird mittels einer Dosierwaage mit einer Zufuhrgeschwindigkeit von 1,16 Masseteilen pro Stunde (MT/h) einem Doppelschneckenkneter des Typs ZSK 25 (L = 42 D; Temperaturen im Bereich von 175 bis 250 °C; Schneckendrehzahl: 300 U/min) der Firma Werner & Pfleiderer, ausgerüstet mit einer Unterwassergranulierung (UWG), zugeführt. Gleichzeitig werden über separate Waagen 5,84 MT/h LLDPE-3-Granulat (Dichte = 0,917 g/cm3; MFR (190/2,16) = 2,3 g/10 min) sowie 3,0 MT/h granulares Propylen/Ethylen(20 Masse-%)-Elastomer mit einer Volumenschmelzflussrate MVR (190/2,16) von 1,2 cm3/10 min (PER*), dem zuvor 0,88 Masse-% Irganox 1330 (Hersteller: Ciba) beigemischt worden sind, zudosiert.The powdery solid phase product obtained in the first step Bspl.-Nr. 1 is fed by means of a dosing with a feed rate of 1.16 parts by mass per hour (MT / h) a ZSK 25 twin screw kneader (L = 42 D, temperatures in the range of 175 to 250 ° C, screw speed: 300 rev / min) Company Werner & Pfleiderer, equipped with an underwater granulation (UWG) supplied. At the same time, 5.84 MT / h of LLDPE-3 granules (density = 0.917 g / cm 3 , MFR (190 / 2.16) = 2.3 g / 10 min) and 3.0 MT / h of granular granules are obtained via separate scales propylene / ethylene (20 mass -%) - elastomer having a melt volume flow rate MVR (190 / 2.16) of 1.2 cm 3/10 min (PER *), the above 0.88% by mass of Irganox 1330 (manufactured by Ciba ) were added, metered.

Entsprechend o. a. Masseverhältnis zwischen dem Festphasenpfropfprodukt, LLDPE-3-Granulat und PER* erfolgt die reaktive Extrusion bei einem mittleren Durchsatz von 10 MT/h.Corresponding to o. A. Mass ratio between the solid phase graft product, LLDPE-3 granules and PER * is the reactive extrusion at a mean throughput of 10 MT / h.

Der aus der Extruderdüse mit einer Temperatur TM von 207 °C austretende Produktstrang wird mittels UWG abgeschlagen. Nach Trocknung des Granulates werden folgende Kennwerte ermittelt (Beispiel 13):

  • MFR (190 °C/5 kg) = 2,7 g/10 min und
  • Maleinierungsgrad CS ex = 0,25 Masse-%
The extruded from the extruder die with a temperature T M of 207 ° C product strand is knocked off by means of UWG. After drying the granulate, the following characteristic values are determined (Example 13):
  • MFR (190 ° C / 5 kg) = 2.7 g / 10 min and
  • Degree of malalination CS ex = 0.25 mass%

In der 2. Pfropfstufe werden außer den in der 1. Stufe pfropfmodifizierten Ethylenpolymeren nachfolgende Ethylenpolymer-Pfropfsubstrate:

  • LLDPE-3 mit Dichte = 0,917 g/cm3 und MFR (190/2,16) = 2,3 g/10 min
  • LLDPE-4 mit Dichte = 0,922 g/cm3 und MFR (190/2,16) = 4,9 g/10 min
  • HDPE-2 mit Dichte = 0,962 g/cm3 und MFR (190/2,16) = 0,5 g/10 min
  • PE-Blend (Reaktorblend der Zusammensetzung: 40 Ma.-% LLDPE und 60 Ma.-% HDPE) mit MFR (190/2,16) = 0,8 g/10 min
sowie nachfolgende Olefinelastomere (jeweils 0,88 Masse-% Irganox 1330 enthaltend) eingesetzt:
  • PER* mit Dichte = 0,855 g/cm3 und MVR (190/2,16) von 1,2 cm3/10 min
  • EOR*-1 mit Dichte = 0,868 g/cm3 und MFR (190/2,16) von 0,5 g/10 min
  • EOR*-2 mit Dichte = 0,870 g/cm3 und MFR (190/2,16) von 5 g/10 min.
In the 2nd grafting step, besides the ethylene polymers graft-modified in the 1st step, the following ethylene polymer graft substrates are:
  • LLDPE-3 with density = 0.917 g / cm 3 and MFR (190 / 2.16) = 2.3 g / 10 min
  • LLDPE-4 with density = 0.922 g / cm 3 and MFR (190 / 2.16) = 4.9 g / 10 min
  • HDPE-2 with density = 0.962 g / cm 3 and MFR (190 / 2.16) = 0.5 g / 10 min
  • PE blend (reactor blend composition: 40 wt% LLDPE and 60 wt% HDPE) with MFR (190 / 2.16) = 0.8 g / 10 min
and subsequent olefin elastomers (each containing 0.88% by weight of Irganox 1330):
  • PER * with density = 0.855 g / cm 3 and MVR (190 / 2.16) of 1.2 cm 3/10 min
  • EOR * -1 with density = 0.868 g / cm 3 and MFR (190 / 2.16) of 0.5 g / 10 min
  • EOR * -2 with density = 0.870 g / cm 3 and MFR (190 / 2.16) of 5 g / 10 min.

In Tabelle 2 sind aufgeführt: Spalte 1: Beispiel-Nummer Spalte 2: Konzentration an eingesetztem Festphasenpfropfprodukt mit Angabe der entsprechenden Bspl.-Nr./Tabelle 1, in Masseteile pro Stunde [MT/h] Spalte 3: Art und Konzentration an eingesetztem LLDPE-HMw, HDPE-HMw oder LLDPE/HDPE-Blend-HMw (PE-HMw), in [MT/h] Spalte 4: Art und Konzentration an eingesetztem Olefinelastomer in [MT/h] Spalte 5: an ZSK-Düse gemessene mittlere Massetemperatur (TM), in [°C] Spalte 6: Schmelzflussrate MFR (190 °C/5 kg), in g/10 min [g/10'] Spalte 7: Gepfropfter Carbonsäuregehalt (CSex), in Masse-% [Ma.-%] Spalte 8: Haft- bzw. Schälfestigkeit (peel strength), in [N/mm] Table 2 lists: Column 1: Example Number Column 2: Concentration of solid phase graft product used, specifying the corresponding Bspl.-Nr./Table 1, in parts by weight per hour [MT / h] Column 3: Type and concentration of LLDPE-HM w , HDPE-HM w or LLDPE / HDPE-Blend-HM w (PE-HM w ), in [MT / h] Column 4: Type and concentration of olefinic elastomer used in [MT / h] Column 5: measured at ZSK nozzle average melt temperature (T M ), in [° C] Column 6: Melt flow rate MFR (190 ° C / 5 kg), in g / 10 min [g / 10 '] Column 7: Grafted carboxylic acid content (CS ex ), in mass% [wt.%] Column 8: Peel strength, in [N / mm]

Der gepfropfte MSA- oder AS-Gehalt CSex, d. h. der Pfropfgrad (auch als Carboxylierungs- oder bei der MSA-Pfropfung als Maleinierungsgrad bezeichnet) ist mittels Rücktitration der durch den Anteil an Carbonsäure (MSA oder AS) nicht neutralisierten Kalilauge wie folgt bestimmt worden:
Nach Behandlung über 6 h bei 80 °C des im siedenden Methanol erhaltenen Rückstandes einer 2 g-Pfropfproduktprobe mit einer Mischung aus 100 ml wassergesättigtem Xylol und 20 ml 0,1-molarer methanolischer Kalilauge - nach Zugabe einiger Tropfen einer 1 %-igen methanolischen Phenolphthaleinlösung - Titration mit 0,1-molarer Salzsäure.The grafted MSA or AS content CS ex , ie the degree of grafting (also referred to as carboxylation or in MSA grafting as Maleinierungsgrad) has been determined by means of back-titration of not neutralized by the proportion of carboxylic acid (MSA or AS) potassium hydroxide solution as follows :
After treatment for 6 h at 80 ° C of the residue obtained in boiling methanol of a 2 g graft product with a mixture of 100 ml of water-saturated xylene and 20 ml of 0.1 molar methanolic potassium hydroxide - after adding a few drops of a 1% methanolic phenolphthalein solution - Titration with 0.1 molar hydrochloric acid.

Die Schmelzflussraten MFR (190 °C/5 kg Auflagegewicht) sind nach ISO 1133 ermittelt worden.The melt flow rates MFR (190 ° C / 5 kg application weight) have been determined according to ISO 1133.

In Tabelle 2 sind die Schmelzepfropf-Parameter sowie die erhaltenen MFR- und CSex-Werte für die aus den oben genannten Komponenten bestehenden carboxylierten Ethylen(co)polymer-Systeme angeführt.Table 2 lists the melt-grafting parameters as well as the MFR and CS ex values obtained for the carboxylated ethylene (co) polymer systems consisting of the above-mentioned components.

Darüber hinaus ist in Tabelle 2 ein Kennwert für die Haftfestigkeit (modifizierte Schälfestigkeit, peel strength) als die für die Bewertung der erfindungsgemäßen carboxylierten Ethylencopolymerblends wesentliche Eigenschaft angegeben. Tabelle 2 Bspl. Extruder-Fahrweise Kennwerte Nr. Festphasen-produkt-Tab.1 [MT/h] PE-HMw [MT/h] Olefin-elastomer [MT/h] TM [°C] MFR (190/5) [g/10'] CSex [Ma.-%] Schälfestigkeit [N/mm] 13 1,16 Nr.1 5,84 LLDPE-3 3,0 PER* 207 2,7 0,25 7,2 Vgl. 13A - 6,94 LLDPE-3 + 0,05 MSA + 0,01 DHBP 3,0 PER* 207 0,2 0.20 3,1 14 1,16 Nr.2 5,84 LLDPE-4 3,0 EOR*-1 215 5,5 0,26 7,0 15 1,4 Nr.3 7,0 HDPE-2 3,6 EOR*-2 215 2,6 0,27 6,8 Vgl. 15A - 8,33 HDPE-2 + 0,06 MSA + 0,01 DHBP 3,6 EOR*-2 216 nicht meßbar (fließt nicht) 0,22 3,0 16 1,16 Nr.4 5,84 PE-Blend 3,0 PER* 219 4,7 0,24 7,8 17 2,5 Nr.4 7,5 LLDPE-4 3,0 EOR*-2 212 4,1 0,27 6,4 18 2,5 Nr.4 4,5 PE-Blend 3,0 PER* 210 6,7 0,23 7,9 Vgl. 18A - 6,94 PE-Blend + 0,05 MSA + 0,012 DHBP 3,0 PER* 212 nicht meßbar (fließt nicht) 0,18 4,1 19 1,16 Nr.5 5,84 HDPE-2 3,0 PER* 224 1,0 0,27 6,2 20 1,4 Nr.6 7,0 LLDPE-4 3,6 PER* 212 5,6 0,23 6,0 21 0,3 Nr.7 6,7 LLDPE-3 3,0 EOR*-1 210 2,5 0,21 4,6 22 0,36 Nr.8 8,04 PE-Blend 3,6 EOR*-1 212 1,6 0,23 4,8 Vgl. 22A - 6,94 PE-Blend + 0,05 MSA + 0,01 DHBP 3,0 EOR*-1 212 nicht meßbar (fließt nicht) 0,17 3,1 23 0,8 Nr.8 6,7 PE-Blend 2,5 EOR*-2 220 2,1 0.61 6,1 24 1,74 Nr.9 8,76 HDPE-2 4,5 PER* 210 1,5 0,37 3,5 25 1,16 Nr.10 5,84 LLDPE-4 3,0 EOR*-1 209 2,8 0,49 6,2 26 2,5 Nr.11 7,5 LLDPE-3 3,0 EOR*-2 207 2,2 0,23 5,4 27 1,16 Nr.12 5,84 PE-Blend 3,0 PER* 210 3,6 0,33 3,8 In addition, in Table 2, a characteristic value for the peel strength ( peel strength ) is given as the property essential for the evaluation of the carboxylated ethylene copolymer blends of the present invention. Table 2 Ex. Extruder driving characteristics No. Solid Phase Product Tab.1 [MT / h] PE-HM w [MT / h] Olefin-elastomer [MT / h] T M [° C] MFR (190/5) [g / 10 '] CS ex [% by weight] Peel strength [N / mm] 13 1,16 No.1 5.84 LLDPE-3 3.0 PER * 207 2.7 0.25 7.2 See 13A - 6.94 LLDPE-3 + 0.05 MSA + 0.01 DHBP 3.0 PER * 207 0.2 12:20 3.1 14 1,16 no.2 5.84 LLDPE-4 3.0 EOR * -1 215 5.5 0.26 7.0 15 1.4 No. 3 7.0 HDPE-2 3.6 EOR * -2 215 2.6 0.27 6.8 See Fig. 15A - 8.33 HDPE-2 + 0.06 MSA + 0.01 DHBP 3.6 EOR * -2 216 not measurable (does not flow) 0.22 3.0 16 1,16 No.4 5.84 PE blend 3.0 PER * 219 4.7 0.24 7.8 17 2.5 No.4 7.5 LLDPE-4 3.0 EOR * -2 212 4.1 0.27 6.4 18 2.5 No.4 4.5 PE blend 3.0 PER * 210 6.7 0.23 7.9 See 18A - 6.94 PE blend + 0.05 MSA + 0.012 DHBP 3.0 PER * 212 not measurable (does not flow) 0.18 4.1 19 1.16 no.5 5.84 HDPE-2 3.0 PER * 224 1.0 0.27 6.2 20 1.4 No.6 7.0 LLDPE-4 3.6 PER * 212 5.6 0.23 6.0 21 0.3 No.7 6.7 LLDPE-3 3.0 EOR * -1 210 2.5 0.21 4.6 22 0,36 No.8 8.04 PE blend 3.6 EOR * -1 212 1.6 0.23 4.8 See 22A - 6.94 PE blend + 0.05 MSA + 0.01 DHBP 3.0 EOR * -1 212 not measurable (does not flow) 0.17 3.1 23 0.8 No.8 6.7 PE blend 2.5 EOR * -2 220 2.1 0.61 6.1 24 1.74 No.9 8.76 HDPE-2 4.5 PER * 210 1.5 0.37 3.5 25 1.16 No.10 5.84 LLDPE-4 3.0 EOR * -1 209 2.8 0.49 6.2 26 2.5 No.11 7.5 LLDPE-3 3.0 EOR * -2 207 2.2 0.23 5.4 27 1,16 no.12 5.84 PE blend 3.0 PER * 210 3.6 0.33 3.8

Zum Vergleich sind in Tabelle 2 - ohne Vorlage eines in der Festphase gepfropften Ethylen(co)polymers - vier allein in der Schmelze hergestellte pfropfcarboxylierte Ethylen(co)polymere mitangeführt (Beispiele Vgl.13A, Vgl.15A, Vgl.18A und Vgl.22A), wobei im Unterschied zu den erfindungsgemäßen Beispielen anstelle des in der 1. Stufe hergestellten Pfropfproduktes in den Extrudereinzug das MSA und der Initiator DHBP, eingemischt in einem Teil des jeweils verwendeten PE-HMw, zugeführt wird. Demnach sind gemäß Bspl.-Vgl.13A über die erste Waage eine Mischung aus 1,10 MT/h LLDPE-3, 0,05 MT/h MSA und 0.01 MT/h DHBP und über eine zweite Waage 5,84 MT/h reines LLDPE-3 zugeführt worden. Entsprechend ist bei den drei anderen Vergleichsbeispielen verfahren worden.By way of comparison, in Table 2 - without the presence of a grafted solid phase ethylene (co) polymer - four graft-carboxylated ethylene (co) polymers prepared by melt alone are included (Examples Vgl.13A, Vgl.15A, Vgl.18A and Vgl.22A) wherein the MSA and the initiator DHBP, mixed into a part of the PE-HM w used in each case, is supplied in contrast to the inventive examples, instead of the prepared in the 1st stage graft into the extruder intake). Accordingly, according to Bspl.-Cgl.13A on the first balance a mixture of 1.10 MT / h LLDPE-3, 0.05 MT / h MSA and 0.01 MT / h DHBP and 5.84 MT / h over a second balance pure LLDPE-3 has been supplied. The same procedure has been followed in the other three comparative examples.

Als Haftfestigkeits-Kennwert ist die in einer Material-Prüfmaschine TC-FR010TH.A5V der Firma Zwick GmbH & Co. an eingespannten Proben aus Aluminiumblechstreifen/0,3 mm Haftvermittler-Folie/Aluminiumblechstreifen-Verbunden (AI/HV/AI) mit einer Zuggeschwindigkeit von 100 mm/min ermittelte Schälfestigkeit verwendet worden.As a bond strength characteristic is in a material testing machine TC-FR010TH.A5V the company Zwick GmbH & Co. clamped to samples of aluminum sheet strips / 0.3 mm adhesive film / aluminum sheet strip composite (AI / HV / AI) with a pulling speed peel strength determined at 100 mm / min.

Die mittels UWG erhaltenen Granulate werden nach ihrer Trocknung zu 0,3 mm dicken Folien extrudiert, in Streifen mit einer Länge von 80 mm und einer Breite von 40 mm geschnitten und zwischen zwei Al-Streifen mit gleicher Dimension gelegt. Anschließend erfolgt in einem Wärmeschrank bei 180 °C eine Temperung der AI/HV/AI-Verbunde, die daraufhin nach verschiedenen Lagerzeiten im Wärmeschrank ohne zusätzliche Gewichtsauflage und Druck vermessen werden.After being dried, the granules obtained by means of UWG are extruded into 0.3 mm thick films, cut into strips 80 mm in length and 40 mm in width and placed between two Al strips of the same dimension. Subsequently, in a heating cabinet at 180 ° C, a tempering of AI / HV / AI composites, which are then measured after various storage times in the oven without additional weight and pressure.

Die Messung wird nach einer Lagerzeit von 8 min an den jeweils in drei geschnittenen (13,3 x 80) mm-AI/HV/AI-Probestreifen durchgeführt. Die in Tabelle 2 angegebenen Schälfestigkeiten sind die aus jeweils vier AI/HV/AI-Verbunden (und somit aus insgesamt 12 Probestreifen-Einzelwerten) für ein getestetes Klebemittel erhaltenen Durchschnittswerte.The measurement is carried out after a storage time of 8 minutes on each of three cut (13.3 x 80) mm AI / HV / AI test strip. The peel strengths given in Table 2 are the average values obtained from in each case four Al / HV / Al composites (and thus from a total of 12 sample individual values) for a tested adhesive.

Wie der Vergleich der Pfropfprodukt-Kennwerte in der Gegenüberstellung mit den reinen Schmelzecarboxylierungsprodukten (Bspl. Vgl.13A, 15A,18A und 22A) zeigt, zeichnen sich die erfindungsgemäß hergestellten carboxylierten Ethylenpolymerblends durch hohe Haftfestigkeiten (Schälfestigkeiten) bei gleichzeitig für die Verwendung gut geeigneten Schmelzviskositäten entsprechend MFR (190 °C/5 kg)-Werten zwischen 1 und 7 g/10 min aus.As the comparison of the graft product characteristics with the pure melt carboxylation products (Bspl. Vgl.13A, 15A, 18A and 22A) shows, the carboxylated ethylene polymer blends produced according to the invention are characterized by high adhesive strengths (peel strengths) with melt viscosities which are also well suited for use according to MFR (190 ° C / 5 kg) values between 1 and 7 g / 10 min.

Darüber hinaus ist besonders hervorzuheben, dass die hohen Schälfestigkeiten dieser neuen Haftvermittler auch nach längerer Temperung erhalten bleiben. Dieses auf der erfindungsgemäßen zweistufigen Festphasen-/Schmelzepfropfcarboxylierung basierende Ergebnis konnte nicht erwartet werden.In addition, it should be emphasized that the high peel strengths of these new adhesion promoters are retained even after prolonged heat treatment. This result based on the two-stage solid phase / melt graft carboxylation of the present invention could not be expected.

Claims (4)

  1. Procedure for the manufacture of carboxylated ethylene polymer blends, characterized by in a 1 step, in a fluid mixing reactor, adding to 100 parts by weight (pbw) of solid-fluid particulate ethylene polymer - with an MFR (190°C/2.16 kg load weight) ≥ 20 g/10 min, chosen from among ethylene homopolymers (HDPE-NMx, LDPE-NMw) and/or linear ethylene copolymers of composition ≥ 80-98 wt.-% ethylene/2 to ≤ 20 wt.-% C3-12-olefin units LLDPE-NMw, EOP-NMw) - 0.05-15 pbw of an α,β-ethylenically unsaturated mono and/or dicarboxylic acid or its anhydride (carboxyl monomer), or a monomer mixture containing at least one carboxyl monomer and 0.01-10 pbw of a free radical-forming initiator with a 1 h half-time temperature (THW/1h) of 50-200°C, or adding a corresponding initiator mixture, and graft-polymerizing at reaction temperatures of 30-120°C for 5-120 min and subsequently,
    in a 2nd step, continuously feeding into a reaction extruder 100 pbw of the modified ethylene polymer obtained in the 1st, solid phase step - together with 150-4,000 pbw of an unmodified ethylene polymer or polymer blend with a MFR (190°C12,16 kg load weight) of < 20 g/10 min, chosen from among ethylene homopolymers (HDPE-HMw, LDPE-HMw), or ethylene copolymers of composition ≥ 85-98 wt.-% ethylene/2 to ≤ 15 wt.-%C3-12-olefin units (LLDPE-HMw,), or compounds or reactor blends consisting of LLDPE and HDPE (HDPE/LLDPE-blend-HMw), as well as 0-4,000 pbw of an olefinic elastomer of composition 10-100 wt.-% propylene and 0-90 wt.-% polymerized-in ethylene and/or C4-12-olefin and/or diene units, or based on an ethylene copolymer with 10-80 wt.-% polymerized-in vinyl acetate (EVA) or (meth)acrylic acid ester units (E(M)AE) - via gravimetric dosing devices, into a reaction extruder and reacting at temperatures of 160-260°C such that at the reactor end a graft-modified olefin polymer blend with a carboxylation degree of 0.5-1 wt.-% is continuously discharged.
  2. Procedure for the manufacture of carboxylated ethylene polymer blends according to claim 1, characterized by using maleic acid anhydride (MSA) and/or acrylic acid (AS) or their mixtures as carboxyl monomer, with a comonomer from the group of vinyl aromatics, preferably styrene, and/or the C1-12-alkyl esters of acrylic or methacrylic acid, preferably methyl methacrylate (MMA), or methyl (MA) or ethyl (EA) or butyl acrylate (BA), of composition 99-20 wt.-% carboxyl monomer/1-80 wt.-% comonomer, preferably 90-50 wit.-% MSA and/or AS/10-50 wt.-% styrene, in the solid phase step.
  3. Procedure according to claims 1 and 2, characterized by graft polymerizing in the 1st step, for 100 pbw particulate ethylene polymer - with MFR (190°C/2.16 kg) of 20-1000 g/10 min, chosen from an ethylene homopolymer (HDPE-NMw, LDPE-NMw) and/or a linear ethylene copolymer of composition ≥ 90-98 wit.-% ethylene/2 to ≤ 10 wt.-% C3-8-olefin units (LLDPE*-NMw) - 0.2-12 pbw MSA, alone or as monomer mixture with 0.02-6 pbw styrene, under addition of 0.05-5 pbw of a mixture consisting of at least two radical-forming initiators with different half-time temperatures (THW/1h) of 50-120°C and of 120-180°C, at reaction temperatures of 50-100°C, for a reaction time of 8-80 min and subsequently,
    in a 2nd step, continuously feeding into an extruder a mixture of 100 pbw of the modified ethylene (co)polymer obtained in the 1st step, 180-3600 pbw of an unmodified ethylene polymer or polymer blend with an MFR (190°C/2.16 kg) of 0.1-20 g/10 min, chosen from among ethylene homopolymers (HDPE-HMw, LDPE-HMw) or ethylene copolymers of composition ≥ 90-98 wt.-% ethylene/2 to ≤ 10 wt.-% C3-8-olefin units (LLDPE*-HMw), or HDPE/LLDPE-blends, as well as 100-3,000 pbw of an elastomer (ELPP, PER) consisting of 50-75 wt.-% ethylene and 25-50 wt.-% C3-8-olefin units (EOR), or of 70-100 wt.-% propylene and 0-30 wt.-% ethylene and/or C4-8-olefin units that contains at least one known stabilization agent and/or antioxidant, reacting
    at mass temperatures of 170-250°C and continuously taking from the extruder jet a graft-modified olefin polymer blend with a degree of carboxylation of 0.1-0.6 wit.-%.
  4. Procedure according to claim 3, characterized by the olefinic elastomer containing a primary antioxidant added in a separate mixing step, preferably a compound from the group of sterically hindered phenols, or a combination of in each case at least one primary and one secondary antioxidant, preferably of a system containing a sterically hindered phenolic compound and a phosphite compound, in an amount of 0.01-5 pbw relative to 100 pbw olefin elastomer.
EP08801310A 2007-09-11 2008-09-09 Method for producing carboxylated ethylene polymer blends Active EP2190885B1 (en)

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DE102007043972A DE102007043972B4 (en) 2007-09-11 2007-09-11 Process for the preparation of carboxylated ethylene polymer blends
PCT/DE2008/001506 WO2009033465A2 (en) 2007-09-11 2008-09-09 Method for producing carboxylated ethylene polymer blends

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WO2009033465A3 (en) 2009-05-22
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WO2009033465A2 (en) 2009-03-19
US8742016B2 (en) 2014-06-03
CN101939340A (en) 2011-01-05
DE102007043972A1 (en) 2009-05-20
CA2704736C (en) 2016-04-26
JP5690140B2 (en) 2015-03-25
ATE512167T1 (en) 2011-06-15
EP2190885A2 (en) 2010-06-02
JP2010539258A (en) 2010-12-16
RU2010114263A (en) 2011-10-20
US20110077356A1 (en) 2011-03-31

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